JPWO2007129721A1 - Biaxially oriented polyarylene sulfide film - Google Patents

Abstract

A biaxially oriented polyarylene sulfide film with excellent heat resistance, dimensional stability, electrical properties, and chemical resistance has reduced heat stress at 200 ° C and improved elongation at break to improve heat moldability, film formation stability, and flatness. An excellent biaxially oriented polyarylene sulfide film is provided. It is composed of a polyarylene sulfide resin composition having a melt crystallization temperature of 160 to 220 ° C., comprising 70 to 99 parts by weight of polyarylene sulfide and 1 to 30 parts by weight of other thermoplastic resin A, and the thermoplastic resin A has an average dispersion diameter. A biaxial film having a dispersed phase of 50 to 500 nm, a breaking stress in the longitudinal direction or width direction of the film at 200 ° C. of 30 to 90 MPa, and a breaking elongation in the longitudinal direction or width direction of 200 ° C. of 100 to 250%. Oriented polyarylene sulfide film.

Description

  The present invention relates to a biaxially oriented polyarylene sulfide film having excellent heat resistance, dimensional stability, electrical characteristics, chemical resistance, and excellent moldability and film forming stability. The biaxially oriented polyarylene sulfide film of the present invention is an electric insulating material such as a motor, a transformer, and an insulating cable, a molding material, a circuit board material, a process such as a circuit / optical member, a release film, a protective film, and a lithium ion battery material. It can be used for fuel cell materials, speaker diaphragms and the like. More specifically, it is suitable for electrical insulation materials for water heater motors, electrical insulation materials for car air conditioner motors and drive motors used in hybrid vehicles, and speaker diaphragms for mobile phones. The present invention relates to a biaxially oriented polyarylene sulfide film having excellent heat moldability.

  In recent years, electric insulation materials for motors have been required to have heat resistance and hydrolysis resistance at high temperatures. For example, as an electrical insulation material for motors used in refrigerators and air conditioners, a new alternative refrigerant related to the complete abolition of specific chlorofluorocarbons has been proposed due to environmental problems. In addition to heat resistance, hydrolysis resistance is required. In addition to heat resistance, electrical insulation materials for motors used in hybrid vehicles are required to have hydrolysis resistance because moisture intrudes under the usage environment.

  In addition, vibrations of acoustic equipment using polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) and polyetherimide (PEI), which are superior in heat resistance and rigidity to PET, are used for acoustic equipment diaphragms made of plastic. A board is used.

However, an acoustic device diaphragm using PET, when used for a small-diameter speaker, for example, a cellular phone, is likely to be thermally deformed in an atmosphere of 65 ° C. or higher, and has insufficient heat resistance. On the other hand, an acoustic diaphragm using PEN has better heat resistance than a diaphragm using PET, but it is not sufficient. In an acoustic diaphragm using PEI, depending on the shape of the speaker diaphragm, Rolling and chatter are likely to occur and the acoustic characteristics deteriorate, and when the external output increases, the film cannot withstand and breaks.
Polyarylene sulfide films have excellent heat resistance, flame retardancy, rigidity, chemical resistance, electrical insulation, and low moisture absorption, so polyphenylene sulfide (hereinafter referred to as PPS) Application of film (sometimes abbreviated) and application to speaker diaphragms are underway. For example, it is known that (1) a biaxially oriented film is used as an electrical insulating material (see Patent Document 1). In addition, (2) a film for an acoustic diaphragm made of polyphenylene sulfide (PPS) has been proposed (Patent Document 2).

  However, the conventional films and sheets described above have the following problems. That is, the film of item (1) above may not have sufficient tensile elongation at break and toughness. For example, when used as a slot liner or wedge for a motor, the film may tear. In addition, although it has been proposed to form by heating in order to improve such formability (see Patent Document 3), the PPS film has little reduction in breaking stress due to heating and little improvement in breaking elongation. Therefore, it is difficult to improve the heat moldability. Also in the film of the above item (2), the breaking elongation is small and the improvement in breaking elongation due to heating is small.

As described above, the polyphenylene sulfide film has low tensile fracture elongation and low toughness, and its application is limited at present, and its improvement has been strongly desired. As a method for improving the toughness, a resin composition or film in which another thermoplastic resin is mixed with polyphenylene sulfide has been proposed. For example, a composition in which nylon 11 and nylon 12 are dispersed with an average dispersion diameter of 1 μm or less in PPS (see Patent Document 4), a composition made of PPS, polyamide and epoxy resin (see Patent Document 5), PPS and polyamide Composition (refer to Patent Documents 6 and 7), a film composed of PPS and polyetherimide (refer to Patent Document 8), a film composed of PPS and polysulfone (refer to Patent Document 9), etc. are disclosed. There is no description about a resin composition or a film in which a thermoplastic resin is finely dispersed in a range of 50 to 500 nm, and a reduction in breaking stress and an improvement in breaking elongation due to heating of a polyphenylene sulfide film are not sufficient. In addition, the film formation stability was not sufficient. On the other hand, a resin composition in which polyamide is finely dispersed has been proposed (see Patent Document 10). However, when forming a sheet or a film, the structural stability thereof may not be sufficient, and further, there is no description about an optimal method for forming a biaxially stretched film. Furthermore, a resin composition in which polyetherimide is ultrafinely dispersed has been proposed (see Patent Document 11). This resin composition was not sufficiently improved in heat moldability because the improvement in elongation at break by heating was small.
JP-A-55-35456 JP-A-6-305019 JP-A-6-335960 JP-A-3-81367 JP 59-155462 A JP-A 63-189458 JP 2001-302918 A Japanese Patent Laid-Open No. 4-146935 JP-A-62-112161 JP 2003-113307 A JP 2001-261959 A

  Therefore, the object of the present invention is to heat a biaxially oriented polyarylene sulfide film having excellent heat resistance, dimensional stability, electrical properties, and chemical resistance by reducing the breaking stress at 200 ° C. and by improving the breaking elongation at 200 ° C. It is to provide a biaxially oriented polyarylene sulfide film excellent in moldability, and to provide a biaxially oriented polyarylene sulfide film excellent in film forming stability. The present invention relates to electric insulating materials and molding materials such as motors, transformers, and insulated cables, circuit board materials, processes and release films and protective films for circuits and optical members, lithium ion battery materials, fuel cell materials, speaker diaphragms, etc. More specifically, electrical insulation materials for water heater motors, electrical insulation materials for car air conditioner motors and drive motors used in hybrid vehicles, and cellular phone speakers. It aims at being able to be used conveniently for a diaphragm etc.

In order to achieve the above object, the present invention has the following configuration.
(1) A biaxially oriented polyarylene sulfide film comprising a polyarylene sulfide resin composition having a melt crystallization temperature of 160 ° C. or higher and 220 ° C. or lower and comprising another thermoplastic resin A different from the polyarylene sulfide. The thermoplastic resin A is a dispersed phase having an average dispersion diameter of 50 to 500 nm, and the polyarylene sulfide content is 70 to 99 wt% when the sum of the polyarylene sulfide content and the thermoplastic resin A content is 100 parts by weight. Part, the content of the thermoplastic resin A is 1 to 30 parts by weight, the breaking stress in the longitudinal direction or the width direction of the film at 200 ° C. is 30 MPa or more and 90 MPa or less, the breaking in the longitudinal direction or the width direction of the film at 200 ° C. A biaxially oriented polyarylene sulfide film having an elongation of 100% or more and 250% or less.
(2) The breaking stress in the longitudinal direction and the width direction of the film at 200 ° C. is 30 MPa or more and 90 MPa or less, and the breaking elongation in the longitudinal direction and the width direction of the film at 200 ° C. is 120% or more and 250% or less (1) 2. A biaxially oriented polyarylene sulfide film described in 1.
(3) The biaxially oriented polyarylene sulfide film according to (1), wherein the melt crystallization temperature is 170 ° C. or higher and 220 ° C. or lower.
(4) The breaking stress in the longitudinal direction and the width direction of the film at 200 ° C. is from 30 MPa to 70 MPa, and the breaking elongation in the longitudinal direction and the width direction at 200 ° C. is from 130% to 230% (1) 2. A biaxially oriented polyarylene sulfide film described in 1.
(5) The biaxially oriented polyarylene sulfide film according to (1), which contains silicon atoms composed of siloxane bonds at the interface of the dispersed phase composed of the thermoplastic resin A.
(6) The biaxially oriented polyarylene sulfide film according to any one of (1) to (5), wherein the polyarylene sulfide is polyphenylene sulfide.
(7) The glass transition temperature of the thermoplastic resin A is 150 ° C. or higher and not higher than the melting point of the polyarylene sulfide (the biaxially oriented polyarylene sulfide film described in 1).
(8) A raw material containing 0.05 to 3 parts by weight of a compatibilizer having at least one group selected from the group consisting of polyarylene sulfide, thermoplastic resin A, and an epoxy group, amino group, and isocyanate group. A biaxially oriented polyarylene sulfide film according to 1 is formed by melt-forming a kneaded resin composition.
(9) The biaxially oriented polyarylene sulfide film according to (1), wherein the thermoplastic resin A is at least one polymer selected from the group consisting of polyarylate, polyphenylene ether, polyetherimide, polyethersulfone, and polysulfone.
(10) The biaxially oriented polyarylene sulfide film according to (1), wherein the film has a thickness of 6 μm or more and 500 μm or less.
(11) The biaxially oriented polyarylene sulfide film according to (1), wherein the film has a thickness of 20 μm or more and 500 μm or less.
(12) The biaxially oriented polyarylene sulfide film according to (1), which has a slight endothermic peak immediately below the melting point at 220 ° C. or higher and 280 ° C. or lower.
(13) The method for producing a biaxially oriented polyarylene sulfide film according to (1), wherein an acid-terminated polyarylene sulfide, the thermoplastic resin A and a compatibilizer are melt-kneaded to prepare a master chip, and then the master A method for producing a polyarylene sulfide film obtained by biaxially stretching a composition obtained by melt-kneading a chip and a Na-terminal or Ca-terminal polyarylene sulfide.
(14) The method for producing a biaxially oriented polyarylene sulfide film according to (1), wherein the heat setting after stretching is performed in two or more steps having different temperatures, and the heat setting temperature of the first step is set to 160. -240 degreeC The manufacturing method of the biaxially-oriented polyarylene sulfide film whose maximum temperature of the heat setting process performed after the 2nd step is more than the heat setting temperature of the 1st step and is 220-280 degreeC.

  According to the present invention, as described below, the biaxially oriented polyarylene sulfide film having excellent heat resistance, dimensional stability, electrical properties, and chemical resistance has a 200 ° C rupture stress reduction and rupture elongation improvement. A high-quality biaxially oriented polyarylene sulfide film excellent in heat moldability can be obtained, and a biaxially oriented polyarylene sulfide film excellent in film formation stability can be obtained. In particular, it can be used in electrical insulation materials for water heater motors, electrical insulation materials for car air conditioners and drive motors used in hybrid vehicles, and speaker diaphragms for mobile phones. An excellent biaxially oriented polyarylene sulfide film can be obtained.

  Hereinafter, the biaxially oriented polyarylene sulfide film of the present invention will be described. The biaxially oriented polyarylene sulfide film of the present invention is a biaxially oriented polyarylene sulfide film comprising a polyarylene sulfide and another thermoplastic resin A different from the polyarylene sulfide. When the total content of the plastic resin A is 100 parts by weight, 70 to 99 parts by weight of polyarylene sulfide and 1 to 30 parts by weight of the thermoplastic resin A are included. The thermoplastic resin A forms a dispersed phase, and the average dispersion is 50 to 500 nm. Thereby, the characteristic which the breaking stress fall by heating and the breaking elongation improved can be provided to the film obtained.

  In the biaxially oriented polyarylene sulfide film, when the sum of the contents of the polyarylene sulfide and the other thermoplastic resin A is 100 parts by weight, the polyarylene sulfide is 70 to 97 parts by weight and the thermoplastic resin A is 3 to 30 parts. It is preferable to use parts by weight, more preferably 90 to 95 parts by weight of polyarylene sulfide and 5 to 10 parts by weight of thermoplastic resin A. If the thermoplastic resin A exceeds 30 parts by weight, the heat resistance and chemical resistance of the biaxially oriented polyarylene sulfide may be impaired, and the elongation at break by heating of the present invention may not be obtained. is there. On the other hand, if the thermoplastic resin A is less than 1 part by weight, it may be difficult to lower the breaking stress and improve the breaking elongation due to heating.

  The biaxially oriented polyarylene sulfide film of the present invention has excellent heat moldability as well as excellent heat resistance, chemical resistance, and electrical properties inherent in the polyarylene sulfide film.

  In order to develop such characteristics, it is important that the polyarylene sulfide forms a sea phase (continuous phase or matrix) and the other thermoplastic resin A forms an island phase (dispersed phase). The dispersed phase here is a phase composed of two or more components that can be measured with an optical microscope or an electron microscope, and is a phase dispersed as an island phase in a sea phase that is a continuous phase, and has an interface. The sea and islands are in contact. The shape of the dispersed phase is, for example, a substantially spherical or elongated island shape, a substantially oval shape, or a fiber shape. The shape may be generally the above shape, and the interface between the sea phase and the island phase may be uneven, or may be a multi-leaf shape. Also included are those in which adjacent dispersed phases are bonded to each other. In the biaxially oriented polyarylene sulfide film of the present invention, it is preferable that the dispersed phase is spherical in order to develop the heat moldability improvement of the present invention. The dispersed phase of the present invention can be confirmed using a transmission electron microscope. Furthermore, it is important that the average dispersion diameter of the thermoplastic resin A is 50 to 500 nm, preferably in the range of 70 to 300 nm, and more preferably in the range of 100 to 200 nm. When the polyarylene sulfide forms a continuous phase, the heat resistance, chemical resistance, and electrical properties of the polyarylene sulfide can be greatly reflected in the film. In addition, by setting the average dispersion diameter in the above range, it is possible to obtain a biaxially oriented polyarylene sulfide film having an excellent balance between heat resistance and moldability improvement. If the average dispersion diameter of the dispersed phase is less than 50 nm, the effects of lowering the breaking stress and improving the breaking elongation due to heating of the present invention may not be sufficiently imparted. On the other hand, if the average dispersion diameter is larger than 500 nm, the heat resistance may be deteriorated or the film may be broken during the film-forming stretch. When adjacent dispersed phases are bonded to each other, an average dispersed diameter is calculated with a spherical or elongated island shape, oval shape, or fibrous phase as one dispersed phase.

  The average dispersion diameter of a disperse phase here means the average value of the diameter of a film longitudinal direction, the diameter of a width direction, and the diameter of a thickness direction. The average dispersion diameter can be measured using a transmission electron microscope. For example, a sample is prepared by an ultrathin section method, observed using a transmission electron microscope under a condition of an applied voltage of 100 kV, photographed at a magnification of 20,000 times, and the obtained photograph is imaged on an image analyzer. The average dispersion diameter can be calculated by selecting any 100 dispersed phases and performing image processing (details of the measurement method will be described later).

  The aspect ratio of the dispersed phase is not particularly limited, but is preferably in the range of 1-20. A more preferable range of the aspect ratio of the dispersed phase is 1 to 10, and a more preferable range is 1 to 5. By setting the aspect ratio of these island components in the above range, the biaxially oriented film of the present invention can be stably produced, and a biaxially oriented polyarylene sulfide film with improved breaking elongation by heating is obtained. It is preferable because it is easy. Here, the aspect ratio means the ratio of the average major axis / average minor axis of the dispersed phase. The aspect ratio can be measured using a transmission electron microscope. For example, a sample is prepared by an ultrathin section method, observed using a transmission electron microscope under a condition of an applied voltage of 100 kV, photographed at a magnification of 20,000 times, and the obtained photograph is imaged on an image analyzer. As described above, the aspect ratio can be calculated by selecting arbitrary 100 dispersed phases and performing image processing (details of the measurement method will be described later).

  The polyarylene sulfide referred to in the present invention is a homopolymer or copolymer having a repeating unit of-(Ar-S)-. Ar includes structural units represented by the following formulas (A) to (K).

(R1 and R2 are substituents selected from hydrogen, an alkyl group, an alkoxy group, and a halogen group, and R1 and R2 may be the same or different.)
As the repeating unit of polyarylene sulfide used in the present invention, the structural formula represented by the above formula (A) is preferable, and representative examples thereof include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, and random thereof. Examples thereof include copolymers, block copolymers, and mixtures thereof. Particularly preferred polyarylene sulfides are preferably polyphenylene sulfide (PPS) from the viewpoint of film properties and economy, and preferably include 80 mol% of p-phenylene sulfide units represented by the following structural formula as the main structural unit of the polymer. More preferably, it is a resin containing 90 mol% or more. When the p-phenylene sulfide component is less than 80 mol%, the crystallinity and heat transition temperature of the polymer are low, and the heat resistance, dimensional stability, mechanical properties, dielectric properties and the like, which are the characteristics of PPS, may be impaired.

  In the PPS resin, if the repeating unit is less than 20 mol%, preferably less than 10 mol%, other units containing copolymerizable sulfide bonds may be included. As the repeating unit of less than 20 mol%, preferably less than 10 mol% of the repeating unit, for example, a trifunctional unit, an ether unit, a sulfone unit, a ketone unit, a meta bond unit, an aryl unit having a substituent such as an alkyl group, Examples include biphenyl units, terphenylene units, vinylene units, carbonate units, and the like, and specific examples include the following structural units. One or more of these can coexist. In this case, the structural unit may be either a random type or a block type copolymerization method.

  The melt viscosity of the PPS resin and the PPS resin composition is not particularly limited as long as it can be melt-kneaded, but is in the range of 100 to 2000 Pa · s at a temperature of 315 ° C. and a shear rate of 1,000 (1 / sec). It is preferable that it is in the range of 200 to 1,000 Pa · s.

  The PPS used in the present invention can be obtained by various methods, for example, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or JP-B-52-12240 and JP-A-61-7332. Can be produced by a method for obtaining a polymer having a relatively large molecular weight as described in Japanese Patent Publication No. JP-A.

  In the present invention, the obtained PPS resin is subjected to crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, washing with an organic solvent, hot water, an acid aqueous solution, etc., acid anhydride It can also be used after various treatments such as activation with functional group-containing compounds such as products, amines, isocyanates and functional group disulfide compounds.

  Next, although the manufacturing method of PPS resin is illustrated, in this invention, it is not limited to this in particular. For example, sodium sulfide and p-dichlorobenzene are reacted in an amide polar solvent such as N-methyl-2-pyrrolidone (NMP) at high temperature and high pressure. If necessary, a copolymer component such as trihalobenzene can be included. Caustic potash or alkali metal carboxylate is added as a polymerization degree adjusting agent, and a polymerization reaction is performed at 230 to 280 ° C. After the polymerization, the polymer is cooled, and the polymer is filtered as a water slurry through a filter to obtain a granular polymer. This is stirred in an aqueous solution such as acetate at 30 to 100 ° C. for 10 to 60 minutes, washed several times with ion exchange water at 30 to 80 ° C. and dried to obtain a PPS powder. The powder polymer is washed with NMP at an oxygen partial pressure of 10 torr or less, preferably 5 torr or less, then washed several times with ion exchange water at 30 to 80 ° C., and dried under a reduced pressure of 5 torr or less. Since the polymer thus obtained is a substantially linear PPS polymer, stable stretch film formation becomes possible. Of course, if necessary, other polymer compounds, inorganic and organic compounds such as silicon oxide, magnesium oxide, calcium carbonate, titanium oxide, aluminum oxide, crosslinked polyester, crosslinked polystyrene, mica, talc and kaolin and thermal decomposition inhibitors, Heat stabilizers and antioxidants may be added.

  As a specific method for crosslinking / high molecular weight by heating PPS resin, under an oxidizing gas atmosphere such as air or oxygen or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. A method of heating until a desired melt viscosity is obtained at a predetermined temperature in a heating container can be exemplified. The heat treatment temperature is usually selected from 170 to 280 ° C, more preferably from 200 to 270 ° C, and the heat treatment time is usually selected from 0.5 to 100 hours, more preferably from 2 to 50 hours. However, by controlling both of these, a target viscosity level can be obtained. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade, but in order to efficiently and uniformly perform the treatment, use a heating apparatus with a rotary type or a stirring blade. Is preferred.

  As a specific method for heat-treating the PPS resin under an inert gas atmosphere such as nitrogen or under reduced pressure, a heat treatment temperature of 150 to 280 ° C., preferably 200 to 200 ° C. under an inert gas atmosphere such as nitrogen or under reduced pressure. A method of heat treatment at 270 ° C. and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours can be exemplified. The heat treatment apparatus may be a normal hot air drier or a heating apparatus with a rotary or stirring blade, but it is preferable to use a heating apparatus with a rotary or stirring blade for efficient and more uniform treatment. . The PPS resin used in the present invention is preferably a substantially linear PPS that does not undergo high molecular weight by thermal oxidative crosslinking treatment in order to achieve the goal of improving tensile elongation at break.

  The PPS resin used in the present invention preferably contains at least a PPS resin that has been subjected to deionization treatment. Specific examples of the deionization treatment include an acid aqueous solution washing treatment, a hot water washing treatment, and an organic solvent washing treatment, and these treatments may be used in combination of two or more methods.

  The following method can be illustrated as a specific method for the organic solvent cleaning treatment of the PPS resin. That is, the organic solvent is not particularly limited as long as it does not have an action of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, Sulfoxide / sulfone solvents such as dimethyl sulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane, Halogen solvents such as tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, Phenol, cresol, alcohol phenol based solvents such as polyethylene glycol, benzene, and aromatic hydrocarbon solvents such as toluene and xylene. Among these organic solvents, N-methylpyrrolidone, acetone, dimethylformamide and chloroform are particularly preferably used. These organic solvents are used alone or in combination of two or more.

  As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and it is possible to appropriately stir or heat as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning PPS resin with an organic solvent, Arbitrary temperature can be selected in the range of normal temperature-300 degreeC. As the cleaning temperature increases, the cleaning efficiency tends to increase, but usually a sufficient effect is obtained at a temperature of room temperature to 150 ° C. The PPS resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

  The following method can be illustrated as a specific method of the hot water washing process of PPS resin. That is, it is preferable that the water to be used is distilled water or deionized water in order to exhibit a preferable chemical modification effect of the PPS resin by hot water washing. The operation of the hot water treatment is usually performed by adding a predetermined amount of PPS resin to a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the PPS resin to water is preferably larger, but usually a bath ratio of 200 g or less of PPS resin is selected for 1 liter of water.

  The following method can be illustrated as a specific method of the acid aqueous solution washing treatment of the PPS resin. That is, there is a method of immersing the PPS resin in an acid or an acid aqueous solution, and it is possible to appropriately stir or heat as necessary. The acid to be used is not particularly limited as long as it does not have an action of decomposing PPS resin. For example, aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halogen-substituted fatty acids such as chloroacetic acid and dichloroacetic acid. Saturated carboxylic acids, aliphatic unsaturated monocarboxylic acids such as acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid And inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid and silicic acid. Of these, acetic acid and hydrochloric acid are preferably used. It is preferable to wash the acid-treated PPS resin several times with water or warm water in order to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin is not impaired by the acid treatment. When the acid aqueous solution cleaning treatment is performed, the effect of increasing the dispersibility when the PPS resin having an acid terminal is increased or mixing with another thermoplastic resin A and reducing the average dispersion diameter of the dispersed phase is obtained. Since it becomes easy, it is preferable. However, the PPS resin subjected to the acid aqueous solution cleaning treatment (hereinafter sometimes referred to as an acid-terminated PPS resin) has a high melt crystallization temperature, and when the film thickness increases, crystallization occurs on the cast drum after melt extrusion. Since it progresses, film tearing may occur in the subsequent stretching step, and film formation stability may deteriorate.

  On the other hand, it is considered that a PPS resin that has been washed with an aqueous calcium salt solution such as an aqueous calcium acetate solution replaces a part of the terminal component with a Ca terminal component (hereinafter sometimes referred to as a Ca terminal PPS resin). Ca-terminated PPS resins and PPS resins that are not acid-washed (sometimes referred to as Na-terminated PPS resins) have a lower melt crystallization temperature and a lower crystallization speed than acid-terminated PPS resins. When forming a film, it may be preferable to use it as a raw material in order to suppress crystallization of the polymer after melt extrusion. In the present invention, a thick film may be preferably obtained by appropriately adding a Ca-terminated PPS resin or a Na-terminated PPS resin to the acid-terminated PPS resin and appropriately adjusting the ratio thereof. The proportion of the Ca-terminated PPS resin in the total PPS resin is preferably 30% by weight or more and 90% by weight or less, more preferably 40% by weight or more and 90% by weight or less, and further preferably 75% by weight or more. 90% by weight or less. When the proportion of the Ca-terminated PPS resin is less than 30% by weight, crystallization of the PPS resin may proceed at the time of cooling after melt extrusion, film breakage may occur in the stretching process, or heat moldability may deteriorate. There is a case. Moreover, an oligomer component may adhere to the casting drum after melt extrusion or the longitudinal stretching roll, and roll contamination may occur. Moreover, when the ratio of Ca terminal PPS resin exceeds 90 weight%, the dispersibility with the other thermoplastic resin A may deteriorate.

As a method for reducing the oligomer component of the PPS resin, a method of performing preliminary drying before melt extrusion, a method of adding the above-mentioned Ca-terminated PPS in a specified amount of the present invention, and a method of premelting and kneading (pelletizing) are used. A method of kneading (pelletizing) is preferable, and in preliminary kneading, water addition is preferably used for oligomer reduction.
The amount of water added in the preliminary kneading is not particularly limited, but is preferably 0.1% by weight or more and 5% by weight or less from the viewpoint of raw material washing, and more preferably 0.3% by weight or more and 3% by weight or less. More preferably, they are 0.5 weight% or more and 1 weight% or less. When the amount of water added is less than 0.1% by weight, the oligomer component of the melt-extrusion raw material may increase, and casting drum contamination during film formation, wire contamination during electrostatic application, and longitudinal stretching roll contamination may occur. . When the amount of water added exceeds 5% by weight, hopper clogging may occur in the preliminary kneading (pelletizing) step, extrusion stability may be inferior, and productivity may deteriorate.

  The melt crystallization temperature of the PPS resin can be appropriately adjusted depending on the composition of the acid-terminated PPS resin and the Na-terminated or Ca-terminated PPS resin. It is important that the melt crystallization temperature of the biaxially oriented polyarylene sulfide film of the present invention is 155 ° C. or higher and 220 ° C. or lower. More preferably, they are 170 degreeC or more and 220 degrees C or less, More preferably, they are 170 degreeC or more and 200 degrees C or less, Most preferably, they are 170 degreeC or more and 190 degrees C or less. When the melt crystallization temperature is less than 155 ° C., dispersibility with other thermoplastic resins A may be deteriorated. When the melt crystallization temperature exceeds 220 ° C., particularly in a cast film after melt extrusion, particularly a film edge Since the thickness of the portion is increased, crystallization may proceed on the cast drum, and film breakage may occur from the film edge portion crystallized in the stretching process, and film formation stability may deteriorate.

  As another thermoplastic resin A different from the polyarylene sulfide contained in the biaxially oriented polyarylene sulfide film of the present invention, the glass transition temperature of the thermoplastic resin A is 150 ° C. or more and the melting point of the polyarylene sulfide or less. It is preferable to obtain the heat resistance and heat moldability of the biaxially oriented polyarylene sulfide film of the present invention. The glass transition temperature of the thermoplastic resin A is more preferably 170 ° C. or higher and 250 ° C. or lower, and further preferably 190 ° C. or higher and 230 ° C. or lower. When the glass transition temperature of the thermoplastic resin A is less than 150 ° C., the heat resistance of the biaxially oriented polyarylene sulfide may be impaired. When the glass transition temperature of the thermoplastic resin A exceeds the melting point of the polyarylene sulfide, a film is formed. Sexuality may worsen. Examples of the thermoplastic resin A having a glass transition temperature of 150 ° C. or higher include various polymers such as polyarylate, polyetherimide, polyethersulfone, polysulfone, polyphenylene ether, polyamideimide, polycarbonate, and polycycloolefin, and these polymers. A blend containing at least one of the above can be used. In the present invention, the thermoplastic resin A is preferably selected from at least one kind selected from polyetherimide, polyethersulfone, and polysulfone, from the viewpoint of mixability of polyarylene sulfide and manifestation of the effect of the present invention. In particular, polyetherimide is preferably used.

Moreover, while the glass transition temperature (Tg) of the biaxially oriented polyarylene sulfide film of the present invention is observed at 85 ° C. or higher and lower than 95 ° C., it is preferably not observed at 95 ° C. or higher and 135 ° C. or lower. When Tg is less than 85 ° C., the heat resistance of the film is lowered. Moreover, when Tg is observed at 95 ° C. or higher and 130 ° C. or lower, the elongation at break due to heating may decrease, and the thermoformability may decrease.
The polyetherimide used as the other thermoplastic resin A contained in the biaxially oriented polyarylene sulfide film of the present invention is not particularly limited. For example, as shown by the following general formula, the polyimide component contains an ether bond A polymer which is a structural unit to be preferably exemplified.

In the above formula, R1 is a divalent organic group selected from the group consisting of a divalent aromatic or aliphatic group having 2 to 30 carbon atoms, and an alicyclic group, It is the same divalent organic group as R.
Examples of R1 and R2 include aromatic groups represented by the following formula groups:

Can be mentioned.
In the present invention, when a polyetherimide having a glass transition temperature of 250 ° C. or lower is used, the effects of the present invention can be easily obtained. From the viewpoint of compatibility with polyarylene sulfide, melt moldability, and the like, the structural unit represented by the following formula is used. A condensate of 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride with m-phenylenediamine or p-phenylenediamine is preferred.

A polyetherimide having this structural unit is available from GE Plastics under the trade name “Ultem” (registered trademark). For example, “Ultem 1000” and “Ultem 1010” may be mentioned as polyetherimide having a structural unit (former formula) containing a unit derived from m-phenylenediamine. Moreover, “Ultem CRS5000” is mentioned as a polyetherimide having a structural unit (the latter formula) containing a unit derived from p-phenylenediamine.
Other examples of the thermoplastic resin A contained in the biaxially oriented polyarylene sulfide film of the present invention include polysulfone and polyethersulfone containing the same sulfur atom as the polyarylene sulfide in the molecular skeleton. Various known polysulfone and polyethersulfone can be used. From the viewpoint of miscibility with polyarylene sulfide, examples of the terminal group of polyethersulfone include a chlorine atom, an alkoxy group, and a phenolic hydroxyl group. As the thermoplastic resin A, polyphenylene ether having a molecular structure close to that of polyarylene sulfide is preferably exemplified.

In the present invention, from the viewpoint of improving dispersibility with the polyarylene sulfide resin, the carboxyl end group is preferably 4 equivalents / t or more, more preferably 5 equivalents / t as the terminal component of the thermoplastic resin A. It is t or more.
In the present invention, by reducing the breaking stress due to heating and improving the elongation at break, the heat formability is improved, but in order to develop better heat formability, as a compatibilizing agent, epoxy group, amino group The compound having one or more groups selected from isocyanate groups is preferably added in an amount of 0.05 to 3 parts by weight based on 100 parts by weight of the total of polyarylene sulfide and thermoplastic resin A.
Specific examples of such compatibilizers include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4′- Dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2.2.5.5. -Glycidyl ethers of bisphenols such as tetrakis (4-hydroxyphenyl) hexane, those using halogenated bisphenol instead of bisphenol, glycidyl ether type epoxy compounds such as diglycidyl ether of butanediol, glycidyl such as glycidyl phthalate Glycidyl epoxy resins such as ester compounds, glycidylamine compounds such as N-glycidylaniline, linear epoxy compounds such as epoxidized polyolefin and epoxidized soybean oil, cyclic systems such as vinylcyclohexene dioxide and dicyclopentadiene dioxide Non-glycidyl epoxy resin etc. are mentioned. In addition, other novolac type epoxy resins are also included. The novolac type epoxy resin has two or more epoxy groups and is usually obtained by reacting a novolac type phenol resin with epichlorohydrin. Moreover, a novolac type phenol resin is obtained by a condensation reaction of phenols and formaldehyde. Although there is no restriction | limiting in particular as phenols of a raw material, Phenol, o-cresol, m-cresol, p-cresol, bisphenol A, resorcinol, p-tertiary butylphenol, bisphenol F, bisphenol S, and these condensates are mentioned.

  Moreover, the olefin copolymer which has another epoxy group is also mentioned. Examples of the olefin copolymer having an epoxy group (epoxy group-containing olefin copolymer) include an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefinic (co) polymer. . Moreover, the copolymer which epoxidized the double bond part of the olefin polymer which has a double bond in a principal chain can also be used.

  Examples of functional group-containing components for introducing a monomer component having an epoxy group into an olefinic (co) polymer include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. And a monomer containing an epoxy group.

  The method for introducing these epoxy group-containing components is not particularly limited, and methods such as copolymerization with α-olefin and the like, or graft introduction to an olefin (co) polymer using a radical initiator can be used.

  The introduction amount of the monomer component containing an epoxy group is 0.001 to 40 mol%, preferably 0.01 to 35 mol% with respect to the whole monomer as a raw material of the epoxy group-containing olefin copolymer. It is appropriate to be within the range.

  As an epoxy group-containing olefin copolymer particularly useful in the present invention, an olefin copolymer having an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid as a copolymerization component is preferably exemplified. As said alpha olefin, ethylene is mentioned preferably. These copolymers further include α, β-unsaturated carboxylic acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. It is also possible to copolymerize the alkyl ester, styrene, acrylonitrile and the like.

  Such an olefin copolymer may be any random, alternating, block, or graft copolymerization mode.

  An olefin copolymer obtained by copolymerizing an glycidyl ester of an α-olefin and an α, β-unsaturated carboxylic acid is, among others, a glycidyl ester 1 of 60 to 99% by weight of an α-olefin and an α, β-unsaturated carboxylic acid. An olefin copolymer obtained by copolymerizing ˜40% by weight is particularly preferable.

  Specific examples of the glycidyl ester of α, β-unsaturated carboxylic acid include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably used.

  As a specific example of an olefin copolymer having an α-olefin and a glycidyl ester of α, β-unsaturated carboxylic acid as an essential copolymerization component, an ethylene / propylene-g-glycidyl methacrylate copolymer ("g" Representing graft, the same applies hereinafter), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer-g-polystyrene, ethylene-glycidyl methacrylate copolymer-g-acrylonitrile-styrene copolymer Polymer, ethylene-glycidyl methacrylate copolymer-g-PMMA, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / Glycidi methacrylate Copolymers thereof.

  Furthermore, specific examples of the compatibilizing agent include alkoxysilanes having one or more functional groups selected from epoxy groups, amino groups, and isocyanate groups. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds, ureido group-containing alkoxysilane compounds such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldisilane Isocyanato group-containing alkoxysilane compounds such as toxisilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-amino Examples include amino group-containing alkoxysilane compounds such as propyltrimethoxysilane.

An alkoxysilane having one or more functional groups selected from the above-mentioned epoxy group, amino group, and isocyanate group is preferable as the compatibilizer of the present invention. Among them, the alkoxysilane having an isocyanate group is biaxial including the thermoplastic resin A. It is most preferable because it is easy to reduce the coarse dispersion due to poor dispersion of the dispersed phase of the oriented polyarylene sulfide film, the average dispersion diameter can be easily controlled within the preferred range of the present invention, and the effects of the present invention can be easily obtained.
In addition, when an alkoxysilane having one or more functional groups selected from an epoxy group, an amino group, and an isocyanate group is used, a siloxane bond is easily formed between the polyarylene sulfide and the thermoplastic resin A, and the interface of the dispersed phase Siloxane bonds are likely to be present in the vicinity. Silicon atoms can be detected in the vicinity of the interface of the dispersed phase using a TEM-EDX method or the like. In the present invention, it is preferable that a silicon (Si) atom resulting from a siloxane bond is included in the interface of the dispersed phase made of the thermoplastic resin A.
The content of the compatibilizer having one or more functional groups selected from the epoxy group, amino group, and isocyanate group is 100 parts by weight of the sum of the polyarylene sulfide and the thermoplastic resin A content. It is preferable to contain 0.05-3 weight part, More preferably, it is 0.1-1 weight part, More preferably, it is 0.2-0.5 weight part. When the content of the compatibilizer is less than 0.05 parts by weight, the dispersibility of the thermoplastic resin A is deteriorated, and there is a case where the reduction in breaking stress and the improvement in breaking elongation due to heating of the present invention may not be obtained. If the content of the solubilizer exceeds 3 parts by weight, gas may be generated due to the reaction of the unreacted end groups of the compatibilizer during film formation, resulting in frequent film-breaking or a decrease in the elongation at break of the film. There is a case to do.

  In the biaxially oriented polyarylene sulfide film of the present invention, it is most important for developing the thermoformability of the present invention that the breaking stress at 200 ° C. in the longitudinal direction or the width direction of the film is 30 MPa or more and 90 MPa or less. . The biaxially oriented polyarylene sulfide film of the present invention can impart the thermoformability of the present invention by setting the breaking stress in either the longitudinal direction or the width direction of the film within the scope of the present invention. Of course, it is preferable that the average breaking stress in the longitudinal direction and the width direction is within the range of the present invention, and it is further preferable that both the longitudinal direction and the width direction are within the range of the present invention. In the case of the present invention, it is preferably 30 MPa or more and 70 MPa or less, more preferably 30 MPa or more and 60 MPa or less. In order to make the breaking stress at 200 ° C. within the scope of the present invention, the compatibilizer described in the present invention is added within the preferred range of the present invention, so that the average dispersion diameter of the thermoplastic resin A of the present invention is reduced. The range can be controlled and obtained by the production method of the present invention described later. When the breaking stress at 200 ° C. is less than 30 MPa, the heat resistance of the biaxially oriented polyarylene sulfide may be insufficient. When the breaking stress at 200 ° C. exceeds 90 MPa, the film breakage is improved even in the molding process by heating. Without practical use.

  The breaking stress at the time of heating is the stress when the film sample is ruptured by using an Instron type tensile tester and performing a tensile test with the sample cut in the tensile direction between the upper and lower chuck parts. Is measured as the breaking stress. That is, according to the method prescribed in ASTM-D882, the film was measured using an Instron type tensile tester at various temperatures with a tensile speed of 300 mm / min for a film having a sample size of 10 mm width × 100 mm between test lengths. . The measurement is performed for each of 10 samples, and the average value is taken as the breaking stress.

  In addition, the biaxially oriented polyarylene sulfide film of the present invention exhibits the thermoformability of the present invention that the elongation at break in the longitudinal direction or the width direction of the film at 200 ° C. is 100% or more and 250% or less. Is important above. The biaxially oriented polyarylene sulfide film of the present invention can impart the thermoformability of the present invention by setting the elongation at break in either the longitudinal direction or the width direction of the film within the scope of the present invention. Of course, it is preferable that the average breaking elongation in the longitudinal direction and the width direction is within the scope of the present invention, and it is further preferable that both the longitudinal direction and the width direction are within the scope of the present invention. More preferably, they are 120% or more and 250% or less, More preferably, they are 130% or more and 230% or less, Most preferably, they are 150% or more and 210% or less. In order to make the breaking elongation at 200 ° C. within the range of the present invention, the compatibilizer described in the present invention is added within the preferable range of the present invention, so that the average dispersion diameter of the thermoplastic resin A of the present invention is reduced. It can be controlled within the above range, and can be obtained by the production method of the present invention described later. If the elongation at break at 200 ° C. is less than 100%, the film may be damaged during processing or use, or it may not be practically usable. Moreover, in order to obtain a film having a breaking elongation at 200 ° C. exceeding 250%, it is necessary to reduce the stretching ratio in the stretching step, but the film flatness is deteriorated or the heat resistance of the film is insufficient. There is a case. The biaxially oriented polyarylene sulfide film of the present invention can impart the thermoformability of the present invention by setting the elongation at break in either the longitudinal direction or the width direction of the film within the scope of the present invention. The average breaking elongation in the longitudinal direction and the width direction is more preferably within the range of the present invention, and it is most preferable that both the longitudinal direction and the width direction are within the scope of the present invention.

  In the present invention, polyarylene sulfide, other thermoplastic resin A, and a compatibilizing agent may be mixed with polyarylene sulfide and other heat using a high shear mixer with shear stress such as a twin screw extruder. A method of pre-melting and kneading (pelletizing) a mixture of the plastic resin A and the compatibilizer to form a master chip is preferable. When mixing with a twin screw extruder, from the viewpoint of reducing defective dispersion, it is preferable to equip a triple twin screw type or double twin screw type, and the cylinder setting temperature of the kneading part is 200 ° C. to 280 ° C. The temperature range is preferred. A more preferable temperature range is 210 ° C to 260 ° C, and a further preferable temperature range is 220 ° C to 240 ° C. The resin temperature in the kneading part is preferably in the temperature range of 290 to 400 ° C, more preferably 300 to 360 ° C. By setting the temperature range of the kneading part to a preferable range, it is easy to increase the shear stress and the effect of reducing defective dispersion is enhanced, and the dispersion diameter of the dispersed phase can be controlled within the preferable range of the present invention. The residence time at that time is preferably in the range of 1 to 5 minutes. Moreover, it is preferable that screw rotation speed shall be 100-500 rotation / min, More preferably, it is the range of 200-400 rotation / min. By setting the screw rotation speed within a preferable range, high shear stress is easily added, and the dispersion diameter of the dispersed phase can be controlled within the preferable range of the present invention. Further, the ratio of (screw shaft length / screw shaft diameter) of the twin screw extruder is preferably in the range of 20 to 60, more preferably in the range of 30 to 50.

  Further, in the twin screw, it is preferable to provide a kneading part by a kneading paddle or the like in order to increase the kneading force, and the kneading part is preferably formed in a screw shape having two or more, more preferably three or more.

  Further, a method using a supercritical fluid described in Journal of Plastics Processing Society of Japan, “Molding”, Vol. 15, No. 6, pp. 382 to 385 (2003) can be preferably exemplified.

  The timing of adding the compatibilizer is not particularly limited, but it is impregnated with polyarylene sulfide powder and blended with the thermoplastic resin A. When the polyarylene sulfide and the thermoplastic resin A are melt-kneaded, Preferred examples include a method of adding dropwise from the feed port. When blended with polyarylene sulfide and added, it is preferable to sufficiently perform water management before pre-kneading such as mixing with a compatibilizer after removing water adhering to the polyarylene sulfide chip or the granule surface.

  As described above, when acid-terminated polyarylene sulfide is used, the dispersibility and mixing with the thermoplastic resin A is easy to improve. Therefore, the acid-terminated polyarylene sulfide, the thermoplastic resin A, and the compatibilizing agent are kneaded at high shear to obtain thermoplasticity. It is preferable to prepare a master chip in which the resin A is finely dispersed. In this case, in order to adjust the melt crystallization temperature of the polyarylene sulfide of the final film, it is necessary to add a considerable amount of polyarylene sulfide having a low melt crystallization temperature such as Na-terminal or Ca-terminal polyarylene sulfide. The concentration of the thermoplastic resin A in the master chip is preferably sufficiently higher than the concentration of the thermoplastic resin A in the final film.

  In order to obtain a final film composition, a master chip containing a high concentration of thermoplastic resin A and a polyarylene sulfide having a low melt crystallization temperature are kneaded again under high shear conditions to form a raw material chip for film formation, or For example, a method of extruding a master chip and polyarylene sulfide having a low melt crystallization temperature from a film forming die immediately after high shearing at the time of extrusion at the time of film forming may be mentioned.

  In the present invention, when alkoxysilane is used as a compatibilizing agent, an alkoxysilane-derived alcohol may be generated during kneading or extrusion. From the viewpoint of obtaining a resin composition with a small amount of alcohol generated as a raw material for film formation, using a twin-screw extruder having at least two kneading portions, once polyarylene sulfide and thermoplastic resin A After melt-kneading the compatibilizer, a technique of melt-kneading once more is preferable. In addition, in the second and subsequent melt-kneading, it is preferable to add 0.02 part or more, more preferably 0.1 to 5 parts of water with respect to 100 parts by weight of the total of polyphenylene sulfide and thermoplastic resin A. There is a case. By this method, hydrolysis of the alkoxysilane compound is promoted, and the amount of alcohol generated from the resulting resin composition can be reduced. In order to stabilize the film formation, it is possible to remove as much as possible from the raw material chips for film formation obtained by kneading the impurities and oligomers in the polyarylene sulfide, the thermoplastic resin A, and the alcohol generated by the reaction of the compatibilizing agent. For this purpose, it is preferable to provide a vacuum vent after the kneading zone of the extruder during melt kneading. The method of adding water is not particularly limited, but a method of side-feeding water using a liquid feeding device such as a gear pump or a plunger pump from the middle of the extruder, or once melting and kneading and further melting once or more. When kneading, a preferable method is to mix water or side feed from the middle of the extruder.

  Moreover, although the cause at this time is not clear, a biaxially oriented film made of a raw material obtained by melting and kneading all raw materials in one stage without using the above-described two-stage melting and kneading may be inferior in high temperature elongation and may not be preferable. is there.

  The biaxially oriented polyarylene sulfide film of the present invention includes a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a pigment, a dye, a fatty acid ester, and a wax within a range that does not impair the effects of the present invention. Other components such as organic lubricants may be added. In addition, inorganic particles, organic particles, and the like can be added to the biaxially oriented polyarylene sulfide film in order to impart easy slipping, abrasion resistance, scratch resistance, and the like to the film surface. Examples of such additives include clay, mica, titanium oxide, calcium carbonate, kaolin, talc, wet or dry silica, colloidal silica, calcium phosphate, barium sulfate, alumina, zirconia, and other inorganic particles, acrylic acids, styrene And so-called internal particles, surfactants and the like which are precipitated by a catalyst added during the polymerization reaction of polyarylene sulfide.

  Although the thickness of the biaxially oriented polyarylene sulfide film of the present invention varies depending on the use, etc., it is preferably 6 μm or more and 500 μm, more preferably 20 μm or more and 500 μm or less. From the viewpoint of thin film use or workability, More preferably, it is the range of 20-300 micrometers, More preferably, it is the range of 20-200 micrometers.

  Moreover, it is preferable that the biaxially oriented polyarylene sulfide film of the present invention has a minute endothermic peak immediately below the melting point at 220 ° C. or higher and 280 ° C. or lower because the molding process in heating is improved. More preferably, it is 240 degreeC or more and 280 degrees C or less, More preferably, it is 240 degreeC or more and 260 degrees C or less. When the minute endothermic peak just below the melting point is higher than 280 ° C., film cracking may occur in the molding process, and when it is lower than 220 ° C., the thermal shrinkage of the biaxially oriented film increases, and the heat forming process deforms and yields. It may get worse. The minute endothermic peak temperature just below the melting point is a minute endothermic peak that appears before crystal melting by suggestive scanning calorimetry (DSC) measurement, and is observed at a temperature corresponding to the heat treatment temperature of the film. This is because an incomplete part melts.

  In addition, the biaxially oriented polyarylene sulfide film of the present invention may be subjected to any processing such as heat treatment, molding, surface treatment, lamination, coating, printing, embossing and etching, as necessary.

  The application of the biaxially oriented polyarylene sulfide film of the present invention is not particularly limited. For example, the process / separation of electrical insulating materials such as motors, transformers and insulated cables, molding materials, circuit board materials, circuits and optical members, etc. Used for various industrial materials such as mold materials, protective films, lithium ion battery materials, fuel cell materials, speaker diaphragms, etc. More specifically, it is suitable for electrical insulation materials for water heater motors, electrical insulation materials for car air conditioner motors and drive motors used in hybrid vehicles, and speaker diaphragms for mobile phones. it can.

  Next, the method for producing the biaxially oriented polyarylene sulfide film of the present invention was produced using polyphenylene sulfide as the polyarylene sulfide, polyether imide as the thermoplastic resin A, and isocyanate silane as the compatibilizer. The production of a biaxially oriented polyphenylene sulfide film will be described as an example, but it is needless to say that the present invention is not limited to the following description.

  In the case of mixing polyphenylene sulfide, polyetherimide, and compatibilizing agent, a method of pre-melting and kneading (pelletizing) a mixture of the respective resins before melt extrusion is preferably exemplified.

  In the present invention, first, if necessary, the polyphenylene sulfide pellets or granules vacuum-dried at 180 ° C. for 3 hours or more, the compatibilizing agent, and the polyetherimide pellets are mixed at a predetermined ratio to obtain a bent type two-phase. It is supplied to a shaft kneading extruder and melt kneaded to obtain a blend chip. At this time, it is preferable to prepare a blend raw material having a weight fraction of PPS and polyetherimide of 99/1 to 60/40. As the PPS resin to be used, an acid-terminated PPS raw material is preferable. The weight fraction of the compatibilizer to be added is preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of PPS and polyetherimide. The mixing / kneading method of the blend raw material resin composition is not particularly limited, and various mixing / kneading means may be used. For example, each may be separately fed to a melt extruder and mixed, or only powder raw materials may be preliminarily dry mixed using a mixer such as a Henschel mixer, ball mixer, blender or tumbler, and then Alternatively, melt kneading may be performed with a melt kneader. Thereafter, the blended raw material is again charged into a twin-screw kneader together with a Ca-terminated PPS resin, if necessary, with these recovered raw materials and optionally 0.1 wt% to 5 wt% water, and the desired composition is obtained. It is preferable from the viewpoint of improving the quality of the film and the film forming property.

  Then, the resin composition consisting of PPS, polyetherimide and isocyanate silane obtained by the kneading operation, if necessary, the particle master PPS raw material and the recovered raw material after film formation are appropriately mixed at a predetermined ratio, After vacuum drying at 180 ° C. for 3 hours or more, the melting part of the extruder is put into an extruder heated to a temperature of 300 to 350 ° C., preferably 320 to 340 ° C. Thereafter, the molten polymer passed through the extruder is passed through a filter, and the molten polymer is discharged into a sheet form using a die of a T die. The set temperature of the filter part and the die is preferably 3 to 20 ° C higher than the temperature of the melting part of the extruder, more preferably 5 to 15 ° C. By making the temperature of the filter part and the die higher than the temperature of the melting part of the extruder, abnormal stagnation can be suppressed and the preferred dispersion diameter of the present invention can be obtained. This sheet-like material is brought into close contact with a cooling drum having a surface temperature of 20 to 70 ° C. to be cooled and solidified to obtain a substantially non-oriented unstretched film.

  Next, this unstretched film is biaxially stretched and biaxially oriented. Stretching methods include sequential biaxial stretching methods (stretching methods that combine stretching in each direction, such as a method of stretching in the width direction after stretching in the longitudinal direction), and simultaneous biaxial stretching methods (in the longitudinal direction and the width direction). The method of extending | stretching simultaneously), or the method which combined them can be used.

  Here, a sequential biaxial stretching method in which stretching in the longitudinal direction and then in the width direction is performed first is used. The stretching temperature varies depending on the structural components of PPS and other thermoplastic resins A, but will be described below using, for example, a resin composition comprising 95 parts by weight of PPS and 5 parts by weight of polyetherimide.

  The unstretched polyphenylene sulfide film is heated with a heating roll group, and is 2 to 4 times in the longitudinal direction, preferably 2.5 to 3.4 times, more preferably 2.6 to 3.0 times, one step or two or more steps. It is preferable to stretch in multiple stages (MD stretching) to improve moldability. On the other hand, from the viewpoint of improving moldability and flatness, the draw ratio is preferably 2.8 to 3.2 times, more preferably 3.0 to 3.2 times. The stretching temperature is Tg (glass transition temperature of PPS) to (Tg + 50) ° C., preferably (Tg + 5) to (Tg + 50) ° C., more preferably (Tg + 5) to (Tg + 40) ° C., and more preferably (Tg + 10) to (Tg + 30). ) In the range of ° C. Most preferably, it is in the range of (Tg + 15) to (Tg + 30) ° C. Thereafter, it is cooled by a cooling roll group of 20 to 50 ° C. In order to achieve both formability and flatness, it is most preferable to set the stretching ratio to 3.0 to 3.2 times and the stretching temperature (Tg + 15) to (Tg + 30) ° C.

  As a method of stretching in the width direction (TD stretching) following MD stretching, for example, a method using a tenter is common. The both ends of this film are gripped with clips, guided to a tenter, and stretched in the width direction. The stretching temperature is preferably Tg to (Tg + 60) ° C, more preferably (Tg + 5) to (Tg + 50) ° C, and still more preferably (Tg + 10) to (Tg + 40) ° C. Furthermore, in the preheating zone before the stretching zone of TD stretching, the preheating temperature is preferably 3 to 10 ° C. lower than the temperature of TD stretching, more preferably 5 to 7 ° C. To do. By setting the preheating temperature before TD stretching within a preferable range, the molecular chain orientation can be easily controlled within the range of the present invention without excessively proceeding the crystallization of polyarylene sulfide, and the elongation at break and molding processability can be improved. It becomes easier to obtain the improved effect of the present invention. The draw ratio is preferably 2 to 4 times, more preferably 2.4 to 3.0 times, and still more preferably 2.6 to 2.8 times, in order to improve moldability. On the other hand, from the viewpoints of moldability, flatness, and productivity, the draw ratio is preferably 3.0 to 4.0 times, and more preferably 3.3 to 3.7 times. In order to achieve both formability and flatness, it is most preferable to set the stretching ratio to 3.3 to 3.7 times and the stretching temperature (Tg + 10) to (Tg + 40) ° C.

  Next, this stretched film is heat-set under tension. The preferred heat setting temperature is 200 to 280 ° C., more preferably 240 to 280 ° C., and still more preferably 260 to 280 ° C., and the heat setting time is 1 second to 100 seconds, preferably 1 second to 60 seconds, and more. Preferably, it is 1 second to 30 seconds. When the heat setting temperature is less than 200 ° C., the film may be thermally shrunk and deformed in the heat forming, so that the yield may be deteriorated. When the heat setting temperature exceeds 280 ° C., the crystallization and mechanical strength of the film may increase or the elongation at break may decrease, and the heat moldability decreases due to film breakage during the molding process. There is a case.

  A more preferable condition is that the heat setting after stretching is performed in two or more steps having different temperatures from the viewpoint of improving the flatness of the film. The first stage heat setting temperature is preferably in the range of 160 to 240 ° C, more preferably 160 to 220 ° C, and still more preferably 160 to 200 ° C. The heat setting time of the first stage is 1 second to 100 seconds, preferably 1 second to 60 seconds, and more preferably 1 second to 10 seconds. Next, the maximum temperature of the heat setting temperature of the latter stage is preferably not less than the heat setting temperature of the first stage and 220 to 280 ° C., more preferably (heat setting temperature of the first stage + 20 ° C.) and not less than 240 to 280 ° C. It is. The subsequent heat setting time is 1 to 100 seconds, preferably 1 to 60 seconds, more preferably 1 to 10 seconds, and the entire heat setting time is 200 seconds, preferably 120 seconds, more preferably 20 seconds. It is preferable not to exceed.

Further, this film is subjected to relaxation treatment in the width direction in a temperature range of 150 ° C. or higher and below the melting point of polyarylene sulfide, more preferably 200 ° C. or higher and below the melting point of polyarylene sulfide. The relaxation rate is preferably 0.1 to 10%, more preferably 2 to 8%, and still more preferably 2 to 7%. The relaxation treatment time is 1 second to 100 seconds, preferably 1 second to 60 seconds, and more preferably 1 second to 10 seconds. When the relaxation temperature is less than 150 ° C., the film cannot shrink by the relaxation rate, and the planarity of the film may deteriorate. When the melting point of polyarylene sulfide is exceeded, the crystallization of the film proceeds and the thermoformability is reduced. May decrease.
Further, the film is cooled and rolled up to room temperature, if necessary, in the longitudinal and width directions, if necessary, to obtain the desired biaxially oriented polyphenylene sulfide film.

The characteristic value measurement method and effect evaluation method of the present invention are as follows.
(1) Average dispersion diameter of dispersed phase The film is (a) parallel to the longitudinal direction and perpendicular to the film surface, (b) parallel to the width direction and perpendicular to the film surface, and (c) parallel to the film surface. The sample was cut in various directions, and a sample was prepared by an ultrathin section method. In order to clarify the contrast of the dispersed phase, it may be stained with osmic acid, ruthenic acid, phosphotungstic acid, or the like. In the case where the thermoplastic resin A is polyamide, dyeing with phosphotungstic acid was preferably used. The cut surface was observed using a transmission electron microscope (H-7100FA type, manufactured by Hitachi) under the condition of an applied voltage of 100 kV, and a photograph was taken at 20,000 times. The obtained photograph was taken into an image analyzer as an image, 100 arbitrary dispersed phases were selected, and image processing was performed as necessary, whereby the size of the dispersed phase was determined as follows. When there are less than 100 dispersed phases in one image, it is possible to select 100 dispersed phases by observing another cut surface in the same direction. The maximum thickness (la) and the maximum length (lb) in the film thickness direction of the individual dispersed phases appearing on the cut surface of (a), and the film thickness of the individual dispersed phases appearing on the cut surface of (a). Maximum length in the direction (lc), maximum length in the width direction (ld), maximum length in the film longitudinal direction (le) and maximum length in the width direction of each dispersed phase appearing on the cut surface of (c) ( lf) was determined. Next, the shape index I of the dispersed phase I = (number average value of lb + number average value of le) / 2, shape index J = (number average value of ld + number average value of lf) / 2, shape index K = (of la Number average value + number average value of lc) / 2, the average dispersion diameter of the dispersed phase was (I + J + K) / 3.
(2) Glass transition temperature (Tg), melting temperature (Tm), melt crystallization temperature (Tmc), minute endothermic peak (Tmeta) just below the melting point
According to JIS K7121, the glass transition temperature (Tg) was measured as follows using a temperature modulation DSC manufactured by A Instrument.

Measurement condition:
Heating temperature: 270-570K (RCS cooling method)
Temperature calibration: Melting point of high purity indium and tin Temperature modulation amplitude: ± 1K
Temperature modulation period: 60 seconds Temperature rising step: 5K
Sample weight: 5mg
Sample container: Aluminum open container (22 mg)
Reference container: Aluminum open container (18mg)
The glass transition temperature (Tg) was calculated by the following formula.
Glass transition temperature = (extrapolated glass transition start temperature + extrapolated glass transition end temperature) / 2
Also, using a DSC (RDC220) manufactured by Seiko Instruments Inc. as a differential scanning calorimeter and a disk station (SSC / 5200) manufactured by Seiko Instruments Inc. as a data analyzer, 5 mg of a sample was measured from room temperature on an aluminum tray. The temperature was increased to 20 ° C. at a rate of temperature increase of 20 ° C./min. The peak temperature of the endothermic peak observed at that time was defined as the melting temperature (Tm), and the minute endothermic peak immediately below Tm was defined as Tmeta.

Further, 5 mg of a sample was heated on an aluminum tray from room temperature to 350 ° C. at a heating rate of 20 ° C./min, melted and held at 350 ° C. for 5 minutes, and cooled from 350 ° C. to room temperature at 20 ° C./min. The peak temperature of the exothermic peak observed at that time was taken as the melt crystallization temperature (Tmc).
(3) Breaking strength, breaking elongation It measured using the Instron type tensile tester according to the method prescribed | regulated to ASTM-D882. The measurement was performed under the following conditions, and the number of samples was 10 for each sample, and the average value was taken.

Measuring device: Orientec Co., Ltd. film strong elongation automatic measuring device “Tensilon AMF / RTA-100”
Sample size: width 10mm x test length 100mm
Tensile speed: 300mm / min Measurement environment: Temperature 200 ° C
(4) A mold having a deep-drawn portion where the thermoformable film is bent 180 degrees is subjected to molding press at 200 ° C., pressure 0.4 MPa, time 15 seconds, cooled to 100 ° C., and taken out to room temperature. 1000 samples were prepared, and the number of tears and cracks was counted and judged as follows.
<Thermoformability>
A: Number of occurrences of film breaks and cracks is less than 50 B: Number of occurrences of film breaks and cracks 50 to 100 Δ: Number of occurrences of film breaks and cracks 100 to 200 x: Number of occurrences of film breaks and cracks More than 200 (5) flatness Surface treatment is carried out after film-forming heat setting, and a total of 100 biaxially stretched films obtained are randomly selected for A4 size. A swab soaked with water is tilted as much as possible and placed at the center of the surface-treated surface of the film and moved 10 cm. The tip of the cotton swab was completely immersed in a beaker containing water, and the cotton swab was replaced every time one sample was evaluated. The obtained sample surface was determined according to the following criteria.
○: 90 or more sheets get wet without repelling water Δ: 90 to 50 sheets get wet without repelling water ×: less than 50 sheets get wet without repelling water (6) Oligomer adhesion After film formation at 100 kg / hour for 12 hours, the longitudinally stretched preheated No. 1 and No. 2 rolls heated to 92 ° C. were wiped off by exposure to water and judged according to the following criteria.
(Double-circle): Coloring by oligomer adhesion was not confirmed by any preheating roll.
◯: Coloring due to oligomer adhesion was confirmed on the preheating No. 1 roll, but coloring was not confirmed on the No. 2 preheating roll.
(Triangle | delta): The coloring by adhesion of an oligomer was confirmed by the preheating 1st roll and the preheating 2nd roll.
X: A lot of oligomers adhered to the preheating No. 1 roll, and coloring due to oligomer adhesion was also confirmed on the No. 2 preheating roll.
(8) Melt viscosity
Using a flow tester CFT-500 (manufactured by Shimadzu Corporation), measurement was performed at 310 ° C., a preheating time of 5 minutes, and a shear rate of 1,000 / s with a base length of 10 mm and a base diameter of 1.0 mm.

(Reference Example 1) Polymerization of acid-terminated PPS (PPS-1)
In a 70 liter autoclave equipped with a stirrer, 8,267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2,957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2 -Pyrrolidone (NMP) 11,434.50 g (115.50 mol), sodium acetate 2,583.00 g (31.50 mol), and ion-exchanged water 10,500 g were charged to 245 ° C. while passing nitrogen at normal pressure. After gradually heating over about 3 hours to distill 14,780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10,235.46 g (69.63 mol) of p-dichlorobenzene and 9,09.0.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm. The temperature was raised to 238 ° C. at a rate of 6 ° C./min. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After reacting at 270 ° C. for 100 minutes, 1,260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

The contents were taken out, diluted with 26,300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31,900 g of NMP and filtered off. This was washed several times with 56,000 g of ion-exchanged water, filtered and then washed with 70,000 g of 0.05 wt% acetic acid aqueous solution and filtered. After washing with 70,000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS resin had a melt viscosity of 200 Pa · s (310 ° C., shear rate of 1,000 / s), a glass transition temperature of 90 ° C., a melting point of 280 ° C., and a melt crystallization temperature of 230 ° C. .
Reference Example 2 Polymerization of Ca-terminated PPS resin (PPS-2)
A PPS resin was prepared in the same manner as in Reference Example 1 except that a calcium acetate aqueous solution was used instead of the acetic acid aqueous solution in Reference Example 1. The selected PPS resin had a melt viscosity of 200 Pa · s (310 ° C., shear rate 1,000 / s), a glass transition temperature of 90 ° C., a melting point of 280 ° C., and a melt crystallization temperature of 175 ° C. .

(Reference Example 3) Production of PPS / PEI Blend Chip 70 parts by weight of acid-terminated PPS resin produced in Reference Example 1, polyether imide (Ultem 1010 manufactured by GE Plastics) (PEI) (glass transition temperature) as thermoplastic resin A 215 ° C.) 30 parts by weight, and after vacuum drying at 180 ° C. for 3 hours or more, γ-isocyanatopropyltriethoxysilane is used as a compatibilizing agent for 100 parts by weight of the PPS resin and polyetherimide. (Shin-Etsu Chemical Co., Ltd., “KBE9007”) 1.5 parts by weight, heated to 230 ° C., and equipped with three kneading paddle kneading sections with a vented co-rotating twin-screw kneading extruder (Nippon Steel) Made in a factory, screw diameter 30 mm, screw length / screw diameter = 45.5), residence time 90 seconds, screw rotation speed 3 0 ejected in rev / min was melt extruded into strands, cooled at a temperature 25 ° C. water, was prepared immediately cut to PPS / PEI (70/30 wt%) blend chips.
(Example 1)
33 parts by weight of the PPS / PEI (70/30% by weight) blend chip prepared in Reference Example 3 and 67 parts by weight of Ca-terminated PPS resin prepared in Reference Example 2, 0.3 weight of calcium carbonate powder having an average particle size of 1.2 μm The parts were blended and dried under reduced pressure at 180 ° C. for 3 hours, and then supplied to a full flight single screw extruder in which the melting part was heated to 320 ° C. After the polymer melted by the extruder is filtered through a filter set at a temperature of 330 ° C., it is melt-extruded from a die of a T die set at a temperature of 330 ° C. and solidified by cooling while applying an electrostatic charge to a cast drum having a surface temperature of 25 ° C. And the unstretched film was produced.

  This unstretched film was stretched at a magnification of 2.6 times in the longitudinal direction of the film at a temperature of 108 ° C. using a difference in peripheral speed of the roll by using a longitudinal stretching machine composed of a plurality of heated roll groups. . Thereafter, both ends of the film are gripped with clips, guided to a tenter, stretched in the width direction of the film at a stretching temperature of 100 ° C. and a stretching ratio of 2.8 times, and subsequently heat treated at a temperature of 280 ° C. for 20 seconds. went. Thereafter, a 4% relaxation treatment was performed in the transverse direction in a cooling zone controlled at 150 ° C. to cool to room temperature, and then the film edge was removed to prepare a biaxially oriented PPS film having a thickness of 25 μm.

The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has a low breaking stress at 200 ° C, and at 200 ° C. The elongation at break was high, and there was no film breakage or cracking in thermoforming.
(Example 2)
A PPS / PEI (70/30% by weight) blend chip is prepared in the same manner as in Reference 3 except that 2 parts by weight of γ-isocyanate-propyltriethoxysilane (“KBE9007” manufactured by Shin-Etsu Chemical Co., Ltd.) is added as a compatibilizer. did.
The obtained PPS / PEI (70/30 wt.%) Blend chip is mixed with 17 parts by weight of the Ca-terminated PPS resin prepared in Reference Example 2 and 0.3 part by weight of calcium carbonate powder having an average particle size of 1.2 μm. A PPS / PEI (95/5 wt%) blend chip was prepared in the same manner as in Example 1 except that.
The obtained blended chips of PPS / PEI (95/5 wt%) were dried under reduced pressure at 180 ° C. for 3 hours, and then supplied to a full flight single screw extruder whose melting part was heated to 320 ° C. After the polymer melted by the extruder is filtered through a filter set at a temperature of 330 ° C., it is melt-extruded from a die of a T die set at a temperature of 330 ° C. and solidified by cooling while applying an electrostatic charge to a cast drum having a surface temperature of 25 ° C. And the unstretched film was produced.

This unstretched film was stretched at a magnification of 2.8 times in the longitudinal direction of the film at a temperature of 108 ° C. using a circumferential speed difference of the rolls using a longitudinal stretching machine composed of a plurality of heated roll groups. . Thereafter, both ends of the film are gripped with clips, guided to a tenter, stretched in the width direction of the film at a stretching temperature of 100 ° C. and a stretching ratio of 2.8 times, and subsequently heat treated at a temperature of 280 ° C. for 20 seconds. went. Thereafter, a 4% relaxation treatment was performed in the transverse direction in a cooling zone controlled at 150 ° C. to cool to room temperature, and then the film edge was removed to prepare a biaxially oriented PPS film having a thickness of 25 μm.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has a low breaking stress at 200 ° C, and at 200 ° C. The elongation at break was high, and there was no film breakage or cracking in thermoforming.
(Example 3)
50 parts by weight of the PPS / PEI (70/30% by weight) blend chip prepared in Reference Example 3 and 50 parts by weight of the Ca-terminated PPS resin prepared in Reference Example 2, 0.3 weight of calcium carbonate powder having an average particle size of 1.2 μm A PPS / PEI (15 wt%) blend chip was produced in the same manner as in Example 1 except that the parts were blended, and a biaxially oriented PPS film was produced.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. Film tears and cracks in thermoforming decreased.
(Example 4)
A biaxially oriented PPS film was prepared in the same manner as in Example 1 except that the stretching ratio in Example 1 was 2.8 times in the vertical direction and 2.8 times in the horizontal direction.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. As a result, film tears and cracks in thermoforming decreased.
(Example 5)
A biaxially oriented PPS film was produced in the same manner as in Example 1 except that the draw ratio was 3.0 times in the longitudinal direction and 3.0 times in the transverse direction in Example 1.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. As a result, film tears and cracks in thermoforming decreased.
(Example 6)
A biaxially oriented PPS film was prepared in the same manner as in Example 2 except that the stretching ratio in Example 2 was 3.0 times in the vertical direction and 3.0 times in the horizontal direction.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. As a result, film tears and cracks in thermoforming decreased.
(Example 7)
A biaxially oriented PPS film was prepared in the same manner as in Example 2, except that the stretching ratio in Example 2 was 3.2 times in the vertical direction and 3.2 times in the horizontal direction.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. As a result, film tears and cracks in thermoforming decreased.
(Example 8)
23 parts by weight of acid-terminated PPS resin, 67 parts by weight of Ca-terminated PPS resin and 10 parts by weight of polyetherimide (Ultem 1010 manufactured by GE Plastics) (PEI) (glass transition temperature 215 ° C.) as thermoplastic resin A , 0.5 parts by weight of γ-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBE9007”) as a compatibilizer is blended with 100 parts by weight of the PPS resin and polyetherimide, Vented co-rotating twin-screw kneading extruder equipped with three kneading paddle kneading parts, mixed with 0.3 parts by weight of calcium carbonate powder with a diameter of 1.2 μm and heated to 230 ° C. (manufactured by Nippon Steel Works) , Screw diameter 30 mm, screw length / screw diameter = 45.5), residence time 90 seconds, screw rotation speed 300 rpm It was melt extruded and discharged into a strand shape, cooled with water at a temperature of 25 ° C., and immediately cut to prepare a PPS / PEI (90/10 wt%) blend chip.
The obtained PPS / PEI (90/10 wt%) blend chip was produced in the same manner as in Example 1 to produce a biaxially oriented PPS film.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. As a result, film tears and cracks in thermoforming decreased.
Example 9
Example 2 except that 0.7 parts by weight of γ-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBE9007”) is used as a compatibilizing agent with respect to 100 parts by weight of the total of PPS resin and polyetherimide. A biaxially oriented PPS film was prepared in the same manner as described above.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. As a result, film tears and cracks in thermoforming decreased.
(Example 10)
Example 2 except that 0.15 parts by weight of γ-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBE9007”) is used as a compatibilizing agent with respect to 100 parts by weight of the total of PPS resin and polyetherimide. A biaxially oriented PPS film was prepared in the same manner as described above.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. As a result, film tears and cracks in thermoforming decreased.
(Example 11)
Biaxial in the same manner as in Example 2 except that bisphenol A type epoxy resin (“Epicoat” 1004 manufactured by Yuka Shell Epoxy Co., Ltd.) is used as a compatibilizing agent with respect to a total of 100 parts by weight of PPS resin and polyetherimide. An oriented PPS film was produced.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has an increased average dispersion diameter of the polyetherimide resin. , Lowering of breaking stress at 200 ° C. and improvement of breaking elongation were suppressed.
Example 12
A biaxially oriented PPS film was prepared in the same manner as in Example 2 except that polyethersulfone (“RADEL” A-200A manufactured by Amoco) (PES) (glass transition temperature 225 ° C.) was used as the thermoplastic resin A.
The measurement and evaluation results for the configuration and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has an increased average dispersion diameter of the polyethersulfone resin. , Lowering of breaking stress at 200 ° C. and improvement of breaking elongation were suppressed.
(Example 13)
A biaxially oriented PPS film was prepared in the same manner as in Example 2 except that polysulfone (“UDEL” P-1700, manufactured by Amoco) (PSF) (glass transition temperature 190 ° C.) was used as the thermoplastic resin A.
The measurement and evaluation results for the configuration and properties of the obtained biaxially oriented PPS film are as shown in Table 1. In this biaxially oriented PPS film, the average dispersion diameter of the polysulfone resin is increased. The decrease in rupture stress at ℃ and the improvement in rupture elongation were suppressed.
(Example 14)
A biaxially oriented PPS film was prepared in the same manner as in Example 2 except that the thickness of the film in Example 2 was 120 μm. The evaluation results of the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has a low breaking stress at 200 ° C. and the breaking elongation at 200 ° C. The film was high, and there was no film breakage or crack in thermoforming.
(Example 15)
In the same manner as in Example 1 except that 57 parts by weight of the Ca-terminated PPS resin prepared in Reference Example 2 was added to 43 parts by weight of the PPS / PEI (88/12% by weight) blend chip in Example 2, PPS / PEI ( 95/5 wt%) blend chips were prepared.
A biaxially oriented PPS film having a thickness of 25 μm was produced from the obtained PPS / PEI (95/5 wt%) blend chip in the same manner as in Example 2.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has a low breaking stress at 200 ° C, and at 200 ° C. The elongation at break was high, and there was no film breakage or cracking in thermoforming.
(Example 16)
In the same manner as in Example 1 except that 33 parts by weight of the Ca-terminated PPS resin prepared in Reference Example 2 was blended with 67 parts by weight of the PPS / PEI (93/7% by weight) blend chip in Example 2, PPS / PEI ( 95/5 wt%) blend chips were prepared.
A biaxially oriented PPS film having a thickness of 25 μm was produced from the obtained PPS / PEI (95/5 wt%) blend chip in the same manner as in Example 2.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. As a result, film tears and cracks in thermoforming decreased.
(Example 17)
A biaxially oriented PPS film was produced in the same manner as in Example 2 except that the longitudinal draw ratio was 3.2 times and the transverse draw ratio was 3.5 times in Example 2. The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. As a result, film tears and cracks in thermoforming decreased.
(Example 18)
A biaxially oriented PPS film was produced in the same manner as in Example 2 except that the transverse draw ratio in Example 2 was 3.7 times. The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. As a result, film tears and cracks in thermoforming decreased.
Example 19
A biaxially oriented PPS film was prepared in the same manner as in Example 2 except that surface treatment was performed during film formation following film formation heat fixation in Example 2. The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 2. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. However, the thermoforming process was excellent, but as a result of evaluating the flatness, the wettability of water at the center of the film formation was insufficient.

(Example 20) In Example 19, in the heat setting after transverse stretching, the first stage heat setting was performed at 200 ° C for 5 seconds, the second stage heat setting was performed at 280 ° C for 5 seconds, and then the width direction was 4 seconds. A biaxially oriented PPS film was prepared by heat treatment and heat treatment in the same manner as in Example 19 except that 5% limited shrinkage (relaxation) treatment was performed at 260 ° C. The measurement and evaluation results for the configuration and properties of the obtained biaxially oriented PPS film are as shown in Table 2. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. The thermoforming process was excellent and the flatness was further improved.
(Example 21)
In Example 19, in the heat setting after transverse stretching, the first stage heat setting was performed at 200 ° C. for 5 seconds, then the second stage heat setting was performed at 265 ° C. for 5 seconds, and then 260 ° C. over 4 seconds in the width direction. A biaxially oriented PPS film was prepared by heat treatment and heat treatment in the same manner as in Example 19 except that 5% limited shrinkage (relaxation) treatment was performed. The measurement and evaluation results for the configuration and properties of the obtained biaxially oriented PPS film are as shown in Table 2. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. The thermoforming process was excellent and the flatness was further improved.
(Example 22)
Carbonic acid having 83 parts by weight of the Ca-terminated PPS resin prepared in Reference Example 2, 1 part by weight of water and an average particle size of 1.2 μm on 17 parts by weight of the PPS / PEI (70/30 wt%) blend chip obtained in Example 2 A PPS / PEI (95/5 wt%) blend chip was prepared in the same manner as in Example 2 except that 0.3 parts by weight of calcium powder was blended.
A biaxially oriented PPS film was produced from the obtained PPS / PEI (95/5 wt%) blend chip in the same manner as in Example 21. The measurement and evaluation results for the configuration and properties of the obtained biaxially oriented PPS film are as shown in Table 2. This biaxially oriented PPS film has improved breaking stress and breaking elongation at 200 ° C. The thermoforming process was excellent, the flatness was excellent, and the oligomer adhesion on the longitudinally stretched preheating roll was reduced as compared with Example 21.
(Comparative Example 1)
The Ca-terminated PPS resin obtained in Reference Example 2 was vacuum-dried at 180 ° C. for 3 hours or more, and then supplied to a full flight single-screw extruder whose melting part was heated to 320 ° C. The polymer melted in the extruder is filtered through a filter set at a temperature of 330 ° C., then melt-extruded from a die of a T die set at a temperature of 330 ° C., and solidified by cooling while applying an electrostatic charge to a cast drum having a surface temperature of 25 ° C. And the unstretched film was produced.

  This unstretched film was stretched at a magnification of 3.8 times in the longitudinal direction of the film at a temperature of 108 ° C. using a peripheral speed difference of the rolls using a longitudinal stretching machine composed of a plurality of heated roll groups. . Thereafter, both ends of the film are gripped with clips, guided to a tenter, stretched in the width direction of the film at a stretching temperature of 100 ° C. and a stretching ratio of 3.6 times, and subsequently heat treated at a temperature of 280 ° C. for 20 seconds. went. Thereafter, a 4% relaxation treatment was performed in the transverse direction in a cooling zone controlled at 150 ° C. to cool to room temperature, and then the film edge was removed to prepare a biaxially oriented PPS film having a thickness of 25 μm.

The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1, and the film has a high breaking stress at 200 ° C. and a low elongation at break, so that the film is formed in thermoforming. Many tears occurred.
(Comparative Example 2)
90 parts by weight of the acid-terminated PPS resin prepared in Reference Example 1 and 10 parts by weight of polyetherimide (Ultem 1010 manufactured by GE Plastics) (PEI) (glass transition temperature 215 ° C.) as the thermoplastic resin A were blended to prepare PPS. The same as Reference Example 3 except that 2 parts by weight of γ-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBE9007”) is added as a compatibilizer to 100 parts by weight of the resin and the polyetherimide. A PPS / PEI (90/10 wt%) blend chip was prepared.

Blending 5 parts by weight of the obtained PPS / PEI (90/10% by weight) blend chip with 95 parts by weight of the Ca-terminated PPS resin prepared in Reference Example 2 and 0.3 parts by weight of calcium carbonate powder having an average particle size of 1.2 μm The blended chips were dried under reduced pressure at 180 ° C. for 3 hours, and then supplied to a full flight single screw extruder whose melting part was heated to 320 ° C. After the polymer melted by the extruder is filtered through a filter set at a temperature of 330 ° C., it is melt-extruded from a die of a T die set at a temperature of 330 ° C. and solidified by cooling while applying an electrostatic charge to a cast drum having a surface temperature of 25 ° C. And the unstretched film was produced.
This unstretched film was stretched at a magnification of 3.8 times in the longitudinal direction of the film at a temperature of 108 ° C. using a peripheral speed difference of the rolls using a longitudinal stretching machine composed of a plurality of heated roll groups. . Thereafter, both ends of the film are gripped with clips, guided to a tenter, stretched in the width direction of the film at a stretching temperature of 100 ° C. and a stretching ratio of 3.6 times, and subsequently heat treated at a temperature of 280 ° C. for 20 seconds. went. Thereafter, a 4% relaxation treatment was performed in the transverse direction in a cooling zone controlled at 150 ° C. to cool to room temperature, and then the film edge was removed to prepare a biaxially oriented PPS film having a thickness of 25 μm.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1, and the film has a high breaking stress at 200 ° C. and a low elongation at break. Many tears occurred.

A biaxially oriented polyphenylene sulfide film was obtained in the same manner as in Example 1 except that no compatibilizer was added. The obtained biaxially oriented polyphenylene sulfide film was a film insufficient in tensile elongation and moldability as shown in Table 1 as a result of measurement and evaluation of its characteristics.
(Comparative Example 3)
60 parts by weight of the acid-terminated PPS resin prepared in Reference Example 1 and 40 parts by weight of polyetherimide (Ultem 1010 manufactured by GE Plastics) (PEI) (glass transition temperature 215 ° C.) as the thermoplastic resin A are blended. Reference Example 3 except that 0.5 parts by weight of γ-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBE9007”) is blended as a compatibilizing agent with respect to 100 parts by weight of the resin and polyetherimide. In the same manner, a PPS / PEI (60/40 wt%) blend chip was produced.
Biaxially oriented in the same manner as in Example 1 except that 100 parts by weight of the obtained PPS / PEI (60/40% by weight) blend chip was mixed with 0.3 parts by weight of calcium carbonate powder having an average particle size of 1.2 μm. A PPS film was prepared.
The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1, and the film has a high breaking stress at 200 ° C. and a low elongation at break. Many tears occurred. Moreover, since the melt crystallization temperature was high and crystallization of the film edge portion proceeded in the cooling step after melt extrusion, film tearing occurred in the film-forming lateral stretching step.
(Comparative Example 4)
A biaxially oriented PPS film having a thickness of 120 μm was formed in the same manner as in Example 14 except that 83 parts by weight of acid-terminated PPS resin was used instead of 83 parts by weight of Ca-terminated PPS resin. Progressed, film tearing occurred frequently in the stretching process, and film formation was not possible.
(Comparative Example 5)
A biaxially oriented PPS film was prepared in the same manner as in Comparative Example 1, except that the longitudinal stretching temperature was 100 ° C., the longitudinal stretching ratio was 3.8 times, the transverse stretching temperature was 100 ° C., and the transverse stretching ratio was 3.6 times. did. The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1, and the film has a high breaking stress at 200 ° C. and a low elongation at break, so that the film is formed in thermoforming. There were many tears.
(Comparative Example 6)
A biaxially oriented PPS film was prepared in the same manner as in Example 2, except that the longitudinal stretching temperature was 100 ° C., the longitudinal stretching ratio was 3.8 times, the transverse stretching temperature was 100 ° C., and the transverse stretching ratio was 3.6 times. did. The measurement and evaluation results for the structure and properties of the obtained biaxially oriented PPS film are as shown in Table 1, and the film has a high breaking stress at 200 ° C. and a low elongation at break, so that the film is formed in thermoforming. Many tears occurred.

  The biaxially oriented polyarylene sulfide film of the present invention and the laminated polyarylene sulfide sheet comprising the same are electrically insulating materials such as motors, transformers, and insulated cables, molding materials, circuit board materials, circuit / optical members and other process / release materials. In various industrial material applications such as lithium ion battery materials, fuel cell materials, speaker diaphragms, etc., they can be suitably used. In particular, it can be suitably used for an electrical insulation material for a water heater motor, an electrical insulation material for a car air conditioner motor and a drive motor used in a hybrid vehicle, and a speaker diaphragm for a mobile phone.

Claims (14)

A biaxially oriented polyarylene sulfide film comprising a polyarylene sulfide resin composition having a melt crystallization temperature of 160 ° C. or higher and 220 ° C. or lower and comprising another thermoplastic resin A different from polyarylene sulfide, and having thermoplastic properties Resin A is a dispersed phase having an average dispersion diameter of 50 to 500 nm, and when the sum of the contents of polyarylene sulfide and thermoplastic resin A is 100 parts by weight, the content of polyarylene sulfide is 70 to 99 parts by weight, The content of the plastic resin A is 1 to 30 parts by weight, the breaking stress in the longitudinal direction or width direction of the film at 200 ° C. is 30 MPa or more and 90 MPa or less, and the breaking elongation in the longitudinal direction or width direction of the film at 200 ° C. A biaxially oriented polyarylene sulfide film that is 100% or more and 250% or less. The breaking stress in the longitudinal direction and the width direction of the film at 200 ° C is from 30 MPa to 90 MPa, and the breaking elongation in the longitudinal direction and the width direction at 200 ° C is from 120% to 250%. Biaxially oriented polyarylene sulfide film. The biaxially oriented polyarylene sulfide film according to claim 1, wherein the melt crystallization temperature is 170 ° C or higher and 220 ° C or lower. The breaking stress in the longitudinal direction and the width direction of the film at 200 ° C is 30 MPa or more and 70 MPa or less, and the breaking elongation in the longitudinal direction and the width direction of the film at 200 ° C is 130% or more and 230% or less. Biaxially oriented polyarylene sulfide film. 2. The biaxially oriented polyarylene sulfide film according to claim 1, comprising a silicon atom composed of a siloxane bond at the interface of the dispersed phase composed of the thermoplastic resin A. 3. 2. The biaxially oriented polyarylene sulfide film according to claim 1, wherein the polyarylene sulfide is polyphenylene sulfide. The biaxially oriented polyarylene sulfide film according to claim 1, wherein the thermoplastic resin A has a glass transition temperature of 150 ° C. or higher and a melting point of the polyarylene sulfide or lower. Kneading a raw material containing 0.05 to 3 parts by weight of a polyarylene sulfide, a thermoplastic resin A, and a compatibilizer having at least one group selected from the group consisting of an epoxy group, an amino group, and an isocyanate group. The biaxially oriented polyarylene sulfide film according to claim 1, wherein the resin composition is formed by melt film formation. The biaxially oriented polyarylene sulfide film according to claim 1, wherein the thermoplastic resin A is at least one polymer selected from the group consisting of polyarylate, polyphenylene ether, polyetherimide, polyethersulfone, and polysulfone. The biaxially oriented polyarylene sulfide film according to claim 1, wherein the film has a thickness of 6 μm or more and 500 μm or less. The biaxially oriented polyarylene sulfide film according to claim 1, wherein the film has a thickness of 20 μm or more and 500 μm or less. The biaxially oriented polyarylene sulfide film according to claim 1, having a slight endothermic peak immediately below the melting point at 220 ° C or higher and 280 ° C or lower. A method for producing a biaxially oriented polyarylene sulfide film according to claim 1, wherein an acid-terminated polyarylene sulfide, a thermoplastic resin A, and a compatibilizer are melt-kneaded to prepare a master chip, and then the master chip and Na A method for producing a polyarylene sulfide film obtained by biaxially stretching a composition obtained by melt-kneading a terminal or Ca-terminated polyarylene sulfide. It is a manufacturing method of the biaxially oriented polyarylene sulfide film of Claim 1, Comprising: The heat setting after extending | stretching is performed in the process of two or more steps from which temperature differs, The heat setting temperature of the 1st step | paragraph is 160-240 degreeC. The manufacturing method of the biaxially-oriented polyarylene sulfide film whose maximum temperature of the heat setting process performed after the 2nd step is more than the heat setting temperature of the 1st step and is 220-280 degreeC.